A Co-based metal-organic framework (Co-MOF) with a unique three-dimensional starfish-like nanostructure was successfully synthesized using a simple ultrasonic method. After subsequent carbonization and oxidation, a nanocomposite of nitrogen-doped carbon with a Co₃O₄ coating (Co₃O₄@N-C) with a porous starfish-like nanostructure was obtained. The final hybrid exhibited excellent lithium storage performance when evaluated as an anode material in a lithium- ion battery. A remarkable and stable discharge capacity of 795 mAh·g⁻¹ was maintained at 0.5 A·g⁻¹ after 300 cycles. Excellent rate capability was also obtained. In addition, a full Co₃O₄@N-C/LiFePO₄ battery displayed stable capacity retention of 95% after 100 cycles. This excellent lithium storage performance is attributed to the unique porous starfish-like structure, which effectively buffers the volume expansion that occurs during Li⁺ insertion/deinsertion. Meanwhile, the nitrogen- doped carbon coating enhances the electrical conductivity and provides a buffer layer to accommodate the volume change and accelerate the formation of a stable solid electrolyte interface layer.